Manufacture of halogenated derivatives of ethylene polymers



Patented Dec. 30,1941 o 2,268,162 UNITED, STATES PATENT OFFICE azeaiez MANUFACTURE OF HALOGENATED DERIVA- TIVES F ETHYLENE POLYMERS James Robertson -Myles and Francis Stephen Bridson-Jones, Northwich, England, assignors to Imperial Chemical Industries Limited, a corporatioii of Great Britain No Drawing. Application August 14, 1939, Serial No. 290,072. In Great Britain August 23, 193:

4 Claims. (Cl. 26094) This invention relates to the manufacture of gen contents differing by more than a certain halogenated derivatives of normally solid or amount are incompatible, or not readily comsemi-solid polymers of ethylene (which may conpatible. In the case of chlorinated ethylene polytain a small amount of oxygen) suol' as maybe mers, the limiting difierence in chlorine content obtained by subjecting ethylene, with or without 5 appears-to be about 12 per cent, i. e. chlorinated a small content of oxygen, to very high pressure ethylene polymers diiiering in. chlorine content and moderately elevated temperature. by more than about 12 per cent areincompatible' By subjecting such ethylene polymers to the or are not readily compatible. action of one or more halogens or halogen com- The L problem of incompatibility can largely be pounds capable of introducing halogen, for which overcome by the use of ternary, quaternary mixpurpose the ethylene polymers maybe dissolved .tures and the like. Thus with two chlorinated or suspended in halogen-stable media (e. g. carpolymers having a difference of chlorine content bon tetrachloride or acetic acid) halogenated outside the normal compatibility range there may ethylene polymers are obtained. The properties be mixed one or more, chlorinated polymers of of the halogenated ethylene polymers are de- 15 such intermediate chlorine content that the pendent upon the proportion of halogen introternary, etc. mixture is compatible. This method duced, (which may range up to about 70 per cent of mixing is illustrated in Example 5. It appears, by weight in the case of chlorinated ethylene too, that certain properties such as flexibility are polymers) as well as upon the conditions of particularly susceptible to improvement by. makpreparation. The production .of halogenated :0 ing. ternary and higher multi-component mixethylene polymers from normally solid ethylene tures.

polymers is described and claimed in U. S. Pat-v When the mixture is to be used for the producent 2,183,556.- a tion of more or less massive articles, e. g. moulded This invention has as an object to devise a new shapes, or of articles in which transparency or method of manufacturing halogenated ethylene ,ggtranslucency is not required, then complete compoiymers. Afurther object is to devise a method patibility is not absolutely 'essential, and the of manufacturing halogenated ethylene polymers chlorinated ethylene polymers employed may difwhich, for a given halogen content, will yield fer in chlorine content by rather more than the halogenated polymers having improved physical aforesaid 12 per cent. When the mixture is to and mechanical properties compared with exist- 80 be used for the production of articles which are ing ethylene polymers. A still further object is to be transparent or tr nsl n sfilms, the

to provide new halogenated ethylene polymers. initial materials should be chosen so as to be.

Further objects will appear hereinafter. These within the range of complete or su stan a y objects are accomplished by the following invenmp e mp b l y. The mixing operation t 38 can, if desired, be effected in more than one stage.

We have now found that by mixing a halogen- The mixing operation can be carried out in ated ethylene polymer containing a given provarious ways, for example by use of a mixing portion of halogen with one or more containing a mill at a suitable temperature, or by mixing different proportion of halogen, the resulting I solutions of the initial materials (e. g. benzene or product exhibits improved properties compared 0 xylene solutions) and afterwards-evaporating off with. a material prepared by halogenating the solvent or precipitating the mixture ofhaloethylene polymer to the same average halogen senated e hylene P m rs therefrom.

content as the mixture. In other words, for a The following examples illustrate but do not halogenated ethylene polymer material of given limit the invention. halogen content, a better material is obtained by Example 1 mixing two or more halogenated ethylene poly-' mers or diflerent halogen contents thanby di- The ene polymer referred to in thi x rectly halogenating ethylene polymer to th ample was of molecular weight about 15,000.

'qulred halogen content. The properties con- Parts of chlorinated ethylene P ymer containing cerne'd are, in particular, toughness, impact re- 50 44 P cent of chlorine were mixed with 50 parts sistance, creep resistance, tensile strength and chmmated ethylene P ym r n in8 2 softening point, one or more of which are higher, Per cent of chlorine, the ing being efiected at not.

for a givenv halogen content, in the mixed prodbY means 0! a mile! mixing mill- The reuct than in the single or directly-prepared prodlilting P t was homogeneous, had a mean t ntion to the mixing of initial materials pared by chlorinating ethylene polymer to 48 per having as vwide a diflerence in halogen content cent chlorine had a film tensile strength of only as possible. but there is a certain limitation to kg./cm.. Further the sof nin P i f he this by reason. of the fact that products of halo- 60 mixed product was some 12 C. higher than that 55 chlorine content of 48 per. cent, and a film tensile Generally speaking it is advantageous t apply strength of kg./cm.=, whereas a material preof the directly prepared material. The softening points were determined by a ball and film method in which a small steel ball is supported on a horizontal film of the material and the temperature is raised under standard conditions until the ball penetrates the film. The softening point is taken as the temperature at which a given point on the ball passes through the film.

Example 2 r The ethylene polymer referred to in this example is of average molecular weight 17,000. 50

Example 3 The ethylene polymer referred to in this ex-- ample is of average molecular weight 17,000. 40 parts of chlorinated ethylene polymer of chlorine content 42% are mixed with 11 parts chlorinated ethylene polymer of chlorine content 51.5%. The homogeneous product of average chlorine content 44% has a higher tensile strength than astraight chlorinated ethylene polymer of the same chlorine content, the actual figures being 100 kg./cm.=,and '20 kg./cm. The

softening range of the product is higher, 50-70-93 C. compared with 40-60-77 C.

Example 4 The ethylene polymer referred to in this example is of average molecular weight 17,000.

A straight chlorinated ethylene polymer of chlorine content 48.5% is compared with homogeneous mixed chlorinated ethylene polymer products of the same, or nearly the same chlorine contents; The straight material has a tensile strength of 150 kg./cm. and a softening range 50-68-87 C. A material obtained by mixing parts chlorinated ethylene polymer of chlorine content with 70 parts chlorinated ethylene polymer of chlorine content 51.5%, i. e. having an average chlorine content 48%, has a tensile strength 170 kg./cm. and a, softening range 58-79-l05 C. Similarly, a material obtained by mixing 47 parts of 44% chlorinated ethylene polymer with 53 parts of 51.5% chlorinated ethylene polymer, i. e. of overage chlorine content 48%, has a tensile strength of 190 kg./cm. and a softening range 60-80-98 C. Finally, a material obtained by mixing 50 parts of 44% chlorinated ethylene polymer with 50 parts of 54% chlorinated ethylene polymer has a tensile strength 160 leg/cm. and a softening range -80-102 C. e

Example 5 The tensile strength, elongation at break and creep resistance, of three chlorinated ethylene polymers, the initial ethylene polymer being of molecular weight about 17,000, each of 50%, average chlorine content were compared. The three materials were:

A. Straight chlorinated ethylene polymer (C. P.).

B. Mixture of 50 parts of 43% chlorine C. P. and

50 parts of 57% chlorine C. P.

C. Mixture of 33 parts of 43% chlorine C. P., 33

of 50% chlorine C. P. and 33 of 57% chlorine C. P.

Mixing was effected as in Example 1. results were:

M W Tensile Elongation 553 a strength at break Q) KaJcm. Percent B was an incompatible mixture and shows a decreased tensile strength, markedly decreased creep resistance, but an increased flexibility compared with A. C, a compatible mixture, shows a still further increased flexibility, a better creep resistance than A, and a tensile strength higher than B but still slightly below that of A.

Creep resistance in this and other examples was measured by extending a strip of cast films of the material under contant load and constant temperature. The figures quoted are 10 (load in kg./cm. required to produce 10% extension between 10 and 70 minutes after the first application of the load).

' Example 6 The properties of three chlorinated ethylene polymers (the initial ethylene polymer being of molecular weight about 40,000) were compared. The three materials were:

A. Straight chlorinated ethylene polymer (C.

B): chlorine content 51.7%.

B. Binary mixture of equal parts of C.'P.s with 48.6% and 54.6% of chlorine: chlorine content of mixture 51.6%. C. Five-component mixture of equal parts of C. P.s with 46.3, 48.6, 52.7, 53.1 and 55.7% chlorine: chlorine content of mixture 51.4%.

Mixing in each case was effected in a roller mixing mill at a temperature of 80 C.

The materials compared as follows:

- Elonga- Creep Material 32 25 tion at resistance break (25C.)

Km/c'm. Percent A 170 220 46 B 240 250 C- 230 210 240 Example 7 Elonga- Creep Tensile gation at resistance st'engm break (25 0.)

Ky.,cm.2 Percent Single material 175 12 500 Quaternary mixture 300 500 Further, the mixture has a softening tempera- The 2,2ea,1ca ture higher than that of the single material at all points in the softening range, namely.

Example 8 The ethylene polymers referred to in this example have a molecular weight about 18,000. A chlorinated ethylene polymer of chlorine content 55% has an impact strength of 1.9 in the units of The molecular weights mentioned herein were obtained by the method for determining the molecular weights of polymers of high molecular weight devised by H. Staudinger (see Berichte der deutschen chemischen Ges. 1934, 67B, 1247 et seq.) this method being based upon the measurement of the viscosity of a solution of the polymer in a solvent (tetra-hydronaphthalene) As a consequence, the molecular weights mentioned herein will only be as accurate as this method of Y measuring them.

the testing machine. A material is obtained by mixing 2 parts of chlorinated ethylene polymer of chlorine content 59% with 1 part of chlorinated ethylene polymer of chlorine content 47% which, having the same average chlorine content (55%) has an impact strength of 11 units. Both materials are hardand relatively inflexible. The test pieces are in each case cut from compression moulded discs of thickness 0.4-0.5 cms.

Example 9 In the above examples, instead of using chlorinated ethylene polymers we could have used brominated, iodinated, or fluorinated ethylene polymers, and instead of using a simple binary mixture of a highly halogenated and a lowly halogenated polymer,'we could with advantage have used ternary or quaternary mixtures using ethylene polymers with threeor four different halogen contents. By this means it is sometimes possible to overcome the incompatibility between polymers having a difference in halogen content of more than 12 per cent, and toobtain a still further improvement in one or more of the aforesaid properties. Thus, with two polymers having a diiierence in chlorine content outside the normal compatibility range there may be mixed one or more polymers of such intermediate chlorine content that the ternary or quaternary mixture is compatible. 7

The mixtures of halogenated ethylene polyvmers in general exhibit more or less the same gradation of character according to halogen content as. do the directly prepared halogenated polymers, e. g. mixtures containing around 15 to 30 percent of chlorine resemble hard or crepe rubber and those containing around 30 to 40'- per cent are soft and tacky, while those containing between. 42 and 55 per cent of chlorine are tough, flexible, gutta percha-like materials, and those containing upwards of about 55 per cent of chlorine are hard and glassy. The present invention is of particular advantage in connection with the production ofthe halogenated polymers of. threetypes namely, the type having a chlorine range 15 to 30 per cent, the type having the chlorine range of 42 to 55 per cent, and the type having the chlorine range of 55 to 87 per cent.

The mixing operation carrbe carried out by various methods, for example by use of a mixing mill at a suitable temperature, or by mixing solutions of the initial materials (e. g. xylene solutions) and afterwards evaporating off the solvent or precipitating'the mixture of halogenated ethylene polymers therefrom. Any conventional type of mixer may be used in carrying out the first method, e. g. mixers of the kind used in compounding rubber or a Werner-Pfleiderer mixer. As examples of solvents which can be applied in the second method may be quoted trichlorethylene, toluene, xylene, tetra-hydronaphthalene, and as examples of precipitant liquids methyl and ethyl alcohols, acetone, and petroleum ether.

In some of the above examples a softening As many apparently widely different embodiments of'this invention may be made without departing from the spirit and scope thereof, it is to be understood that the invention is not limited to the specific embodiments thereof except as de'- fined in the appended claims.

We claim: e 1. A composition of matter which consists essentially of a homogeneous mixture of halogenated ethylene polymers of different halogen content and which consists preponderately of the product obtained by mixing two diflercnt halogenated ethylene polymers differing in halogencontent by at least 4% and by not more than 12%,- the amounts of said polymers of diiferent halogen content present in the mixture being from about equal parts thereof, to about five.

parts of one and about onepart of the other.

2. The composition of matter set forth in claim 1 in'which the halogen contained in said halogenated ethylene polymers is chlorine.

3. The composition of matter set forth in claim 1 in which said mixture of halogenated ethylene polymers is composed of about 50 parts of chlorinated ethylene polymer containing about 40% chlorine and about 50 parts of chlorinated ethylene polymer, containing about 44% chlorine. e

4. The composition ofmatter set forth in claim 1 in which said mixture of halogenated ethylene. 

